EP0354444A2 - Procédé pour l'introduction d'atome de fluor sur un noyau aromatique par échange nucléophile - Google Patents

Procédé pour l'introduction d'atome de fluor sur un noyau aromatique par échange nucléophile Download PDF

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Publication number
EP0354444A2
EP0354444A2 EP89114161A EP89114161A EP0354444A2 EP 0354444 A2 EP0354444 A2 EP 0354444A2 EP 89114161 A EP89114161 A EP 89114161A EP 89114161 A EP89114161 A EP 89114161A EP 0354444 A2 EP0354444 A2 EP 0354444A2
Authority
EP
European Patent Office
Prior art keywords
process according
phase transfer
salts
dichloro
nitrobenzene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89114161A
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German (de)
English (en)
Other versions
EP0354444B1 (fr
EP0354444A3 (en
Inventor
Ernst Dr. Kysela
Rudolf Dr. Braden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
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Publication of EP0354444A2 publication Critical patent/EP0354444A2/fr
Publication of EP0354444A3 publication Critical patent/EP0354444A3/de
Application granted granted Critical
Publication of EP0354444B1 publication Critical patent/EP0354444B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to a particularly advantageous method for introducing fluorine atoms onto aromatic nuclei by nucelophilic exchange, in particular by exchanging halogen atoms and / or nitro groups.
  • phase transfer catalysts are, for example, quaternary ammonium salts, quaternary phosphonium salts and crown ethers.
  • Salts of metals of the 3rd to 5th main group of the periodic table of the elements and of subgroup elements in question are preferred, particularly preferably chlorides.
  • chromium salts such as CrCl3 x 6H2O
  • iron salts such as FeCl3, cobalt salts such as CoCl2 x 6H2O
  • nickel salts such as NiCl2 x 6H2O
  • copper salts such as CuSO4
  • aluminum salts such as AlCl3, zinc salts such as ZnCl2 and antimony salts such as SbCl3.
  • the metal salts can be used in different proportions. Based on one mole of phase transfer catalyst used, 0.1 to 10 moles of metal salt can be used, for example. This amount is preferably 0.2 to 5 moles, in particular 0.25 to 1 mole.
  • the phase transfer catalyst and the metal salts used in each case can be wholly or partly present as complexes formed in situ, for example as complexes of the type where R independently of one another each represents a binding organic radical, for example in each case C1- to C10-alkyl, and R 'and R ⁇ each represent a C1 to C10 alkyl group or, together with the C atom in between, a saturated carbocyclic ring with a total of 5 to 6 C atoms, in which case m is 1 or R' and R ⁇ together with the C atom in between means a carbocyclic aromatic ring with 6 c atoms, where m then stands for zero, Me a metal ion with n positive charges and Hal means halogen.
  • phase transfer catalyst used in each case and / or the metal salt used in each case can also be introduced in whole or in part in the form of complexes into the reaction mixture.
  • phase transfer catalysts examples include quaternary nitrogen compounds, quaternary phosphorus compounds, pyridinium salts and crown ethers.
  • the first 3 types of catalysts mentioned can, for example, have the formulas [NR4] ⁇ Hal ⁇ , [PR4] ⁇ Hal ⁇ or in which R, R ′, R ⁇ , m and Hal have the meaning given above, correspond.
  • Quaternary nitrogen compounds or pyridinium salts for example methyl-trioctyl-ammonium chloride, tetrabutyl-ammonium chloride, tetrabutyl-ammonium bromide, tetraethylammonium chloride, triethyl-benzyl-ammonium chloride, dimethyl-benzyl-phenyl-ammonium chloride, dimethyldodecyl-benzyl-ammonium chloride, triphenyl-phenyl chloride, triphenyl-ammonium chloride, tetrabutyl-ammonium chloride, tetrabutyl-ammonium chloride, tetrabutyl-ammonium chloride, tetrabutyl-ammonium chloride, tetrabutyl-ammonium chloride -benzyl-phosphonium bromide, N ', N'-dimethylamino-N-benzyl-pyridin
  • the phase transfer catalysts can e.g. in amounts of 0.1 to 20 mol%, based on the starting material. This amount is preferably 0.5 to 5 mol%.
  • the process according to the invention does not always have to be carried out in the presence of solvents. Instead of solvents, an excess of the aromatic compound to be fluorinated can also be used. Good results are often obtained when using nitroaromatics even without solvents. Nevertheless, it is generally preferred to use solvents.
  • Useful solvents are practically all aprotic, dipolar solvents which have a sufficiently high boiling point and are sufficiently inert under the reaction conditions, for example Di methyl sulfoxide, N-methylpyrrolidone, tetramethylene sulfone, benzonitrile, nitrobenzene, dimethylacetamide, ethylene glycol dimethyl ether and diglyme.
  • reaction temperatures for the process according to the invention can e.g. are in the range of 100 to 250 ° C.
  • the process is preferably carried out in the range from 130 to 180 ° C.
  • the potassium fluoride can be used in various amounts. In general, the stoichiometrically required amount or more is used. Large surpluses are not critical, but are not economically viable. It is therefore preferable to use 1.1 to 2 moles of potassium fluoride per mole of fluorine atoms to be introduced.
  • Aromatics with different leaving groups can be used as starting material in the process according to the invention.
  • the leaving groups intended for exchange for fluorine are preferably activated by one or more further -I and / or -M substituents, for example by halogen, CN, CO-halogen, SO2-halogen or CF3.
  • Preferred starting materials contain halogen and / or nitro substituents as leaving groups, for example 1 to 3 chlorine atoms bonded to the aromatic nucleus and / or 1 to 2 nitro groups bonded to the aromatic nucleus.
  • Halogen atoms and / or nitro groups located on the aromatic nucleus are preferably exchanged for fluorine atoms with the process according to the invention.
  • Vessel materials for carrying out the reaction according to the invention are, for example, glass, steels alloyed with nickel and / or chromium and perfluorinated olefin polymers.
  • Perfluorinated olefin polymers e.g. Polytetrafluoroethylene are preferred.
  • metal vessels it cannot be ruled out that metal salts originating from vessel materials may get into the reaction mixture to a small extent. This effect may be desirable in certain circumstances (e.g. if the type and amount of the metal salt formed is useful).
  • All components for the reaction mixture are preferably used in dry or largely anhydrous form. If necessary, small amounts of water present in the reaction mixture can be removed by distillation (if appropriate together with a small proportion of the solvent used) or by azeotropic distillation with an entrainer.
  • the mixture present after the reaction can be worked up in different ways depending on the conditions present therein.
  • the process according to the invention has the surprising advantage that, given the reaction time, it can be carried out at a lower temperature or at a given temperature in a shorter time. That means compared to known methods, a reduction in energy consumption, corrosion and the possibility of decomposition reactions and an extension of the life of the phase transfer catalysts.
  • Example 2 The procedure was as in Example 1, but the nature of the metal salt, the nature of the phase transfer catalyst and the nature of the solvent were varied, and for comparison also examples without metal salt addition and without the addition of a phase transfer catalyst were carried out.
  • Water-containing metal salts were added to the mixture of potassium fluoride and tetramethylene sulfone before distillation to remove the water introduced before the start of the reaction.
  • Example 19 The procedure was as in Example 1, but instead of 3,4-dichloro-nitrobenzene, a corresponding amount of 4-chloro-nitrobenzene was used, instead of methyl-trioctyl-ammonium chloride, a corresponding amount of N ′, N′-dimethylamino-N-2- ethyl-hexyl-pyridinium chloride used and obtained instead of 3-chloro-4-fluoro-nitrobenzene 4-fluoro-nitrobenzene.
  • the phase transfer catalyst was varied (Example 19) and examples without metal salt addition were carried out for comparison (Examples 18 and 20).
  • Table 2 Example No. Metal salt Phase transfer catalyst solvent sales of y% achieved after x hours Yield of 4-fluoro-nitrobenzene [% of theory Th.] Remarks x y 17th CrCl3 x 6 H2O D TMS 6 97 92 18th - D TMS 12 93 91 for comparison 19th CrCl3 x 6 H2O E TMS 8th 99 85 20th - E TMS 12 97 83 for comparison

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP89114161A 1988-08-12 1989-08-01 Procédé pour l'introduction d'atome de fluor sur un noyau aromatique par échange nucléophile Expired - Lifetime EP0354444B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3827436 1988-08-12
DE3827436A DE3827436A1 (de) 1988-08-12 1988-08-12 Verfahren zum einfuehren von fluoratomen an aromatische kerne durch nucleophilen austausch

Publications (3)

Publication Number Publication Date
EP0354444A2 true EP0354444A2 (fr) 1990-02-14
EP0354444A3 EP0354444A3 (en) 1990-08-01
EP0354444B1 EP0354444B1 (fr) 1993-01-20

Family

ID=6360749

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89114161A Expired - Lifetime EP0354444B1 (fr) 1988-08-12 1989-08-01 Procédé pour l'introduction d'atome de fluor sur un noyau aromatique par échange nucléophile

Country Status (4)

Country Link
US (1) US4978769A (fr)
EP (1) EP0354444B1 (fr)
JP (1) JP2847786B2 (fr)
DE (2) DE3827436A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0534317A1 (fr) * 1991-09-21 1993-03-31 Hoechst Aktiengesellschaft Procédé de préparation de composés du benzène chlorés et fluorés par fluorodénitration nucléophile sélective
EP0635482A2 (fr) * 1993-07-21 1995-01-25 Hoechst Aktiengesellschaft Procédé pour la préparation de polyfluoronitrobenzènes
EP0781747A1 (fr) * 1993-01-19 1997-07-02 Bayer Ag Procédé pour la préparation de 2,3,4,5-tétrafluoro-trifluorométhylbenzène
EP0781757A1 (fr) * 1991-10-31 1997-07-02 Abbott Laboratories Procédé de préparation d'acides benzoiques fluorés
WO1999003802A1 (fr) * 1997-07-18 1999-01-28 F2 Chemicals Limited Fluoration catalysee de composes carbonyles
EP0899256A2 (fr) * 1997-08-26 1999-03-03 Nippon Shokubai Co., Ltd. Procédé de préparation de composés organiques fluorés
EP1097914A2 (fr) * 1999-11-05 2001-05-09 Clariant GmbH Procédé de traitement de mélanges réactionnels, obtenu par des réactions d' échange d' halogènes

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992000270A1 (fr) * 1990-06-25 1992-01-09 Hoechst Aktiengesellschaft Procede de production de chlorofluoronitrobenzenes et de difluoronitrobenzenes
ES2083631T3 (es) * 1991-07-17 1996-04-16 Hoechst Ag Procedimiento para la preparacion de clorofluoronitrobencenos.
US5315043A (en) * 1992-02-05 1994-05-24 E. I. Du Pont De Nemours And Company Aromatic nucleophilic fluorination
DE4324368A1 (de) * 1993-07-21 1995-01-26 Hoechst Ag Verfahren zur Herstellung von Fluorbenzonitrilen
US5502235A (en) * 1994-12-28 1996-03-26 Dowelanco Solventless process for making 2,6 difluorobenzonitrile
DE69711220T2 (de) 1996-11-22 2002-10-31 Albemarle Corp Halogenaustausch-reaktionen und ihre anwendungen
US5824827A (en) * 1996-11-22 1998-10-20 Albemarle Corporation Halogen exchange reactions
US5789631A (en) * 1996-11-25 1998-08-04 Albemarle Corporation Production of perhalobenzenes
GB9711588D0 (en) * 1997-06-05 1997-07-30 F2 Chemicals Limited Solvent replacement
US5965781A (en) * 1997-11-21 1999-10-12 Albemarle Corporation Catalysis in halogen exchange reactions
WO2002092608A2 (fr) * 2001-05-17 2002-11-21 Rhodia Chimie Utilisation d'une composition de nature ionique comme reactif de substitution, composition constituant un reactif de fluoration et procede l'utilisant
US6489525B1 (en) 2001-10-05 2002-12-03 Bayer Corporation Methods for preparing primary alkyl bromides
DE10227223A1 (de) * 2002-06-18 2004-01-08 Kühlein, Klaus, Prof.Dr. Verfahren zur Herstellung substituierter organischer Verbindungen und Verwendung von Katalysatoren für Substitutionsreaktionen
ES2431592T3 (es) * 2006-07-18 2013-11-27 The Board Of Regents Of The University Of Nebraska Métodos y agentes para preparar agentes de fluoración radiomarcados con 18F
US20110098326A1 (en) * 2009-10-26 2011-04-28 Pike Victor W 2-fluorothiazole derivatives useful as imaging agents; methods of synthesis, and methods of use
TW201609652A (zh) * 2013-11-12 2016-03-16 陶氏農業科學公司 用於氟化化合物之過程（三）
JP7353013B2 (ja) * 2019-08-29 2023-09-29 フジアン ヨンジン テクノロジー カンパニー リミテッド フルオロベンゼンおよびその触媒の製造プロセス
CN116237029B (zh) * 2023-02-28 2023-09-05 福建省杭氟电子材料有限公司 用于甲烷氟化的光催化剂

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3992432A (en) * 1967-04-05 1976-11-16 Continental Oil Company Phase transfer catalysis of heterogeneous reactions by quaternary salts
EP0003344A1 (fr) * 1978-01-26 1979-08-08 BASF Aktiengesellschaft Procédé de préparation de fluorobenzènes
DE2938939A1 (de) * 1978-10-05 1980-04-17 Boots Co Ltd Verfahren zur herstellung von fluornitrobenzolen
GB2039473A (en) * 1979-01-11 1980-08-13 Dow Chemical Co Reaction of a chlorinated pyridine with an alkali metal fluoride
JPS57197226A (en) * 1981-05-30 1982-12-03 Dainippon Ink & Chem Inc Preparation of aromatic fluorine compound
JPS60130537A (ja) * 1983-12-16 1985-07-12 Asahi Glass Co Ltd 芳香族フツ素化合物の製法
JPS6165830A (ja) * 1984-09-06 1986-04-04 Daikin Ind Ltd フルオロ有機化合物の製法
WO1987004151A1 (fr) * 1986-01-06 1987-07-16 Mallinckrodt, Inc. Preparation de composes fluoroaromatiques dans une dispersion de fluorure de potassium

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1094182A (en) * 1964-02-26 1967-12-06 Imp Smelting Corp Ltd Fluorination of halogenated organic compounds
JPS5726261B2 (fr) * 1973-03-06 1982-06-03
US4071521A (en) * 1976-08-23 1978-01-31 The Dow Chemical Company Process for making 2,6-difluoro pyridine
US4229365A (en) * 1977-05-28 1980-10-21 Basf Aktiengesellschaft Manufacture of substituted fluorobenzenes
JPS579762A (en) * 1980-06-19 1982-01-19 Ishihara Sangyo Kaisha Ltd Production of trifluoromethylpyridine
US4542221A (en) * 1981-05-18 1985-09-17 The Dow Chemical Company Exchanging fluorine for chlorine in a chlorinated pyridine with an alkali metal fluoride
DE3478681D1 (en) * 1983-02-18 1989-07-20 Nippon Catalytic Chem Ind Organic fluorine compounds
JPS59222463A (ja) * 1983-06-02 1984-12-14 Mitsubishi Metal Corp ペンタフルオロベンゾニトリルの製造方法
JPS6072850A (ja) * 1983-09-28 1985-04-24 Tokuyama Soda Co Ltd フッ化ベンゾニトリル類の製造方法
JPS6072851A (ja) * 1983-09-30 1985-04-24 Tokuyama Soda Co Ltd フツ化ベンゾニトリル類の製造方法
US4822887A (en) * 1983-12-23 1989-04-18 The Dow Chemical Company Preparation of difluoropyridine compounds
JPS60184057A (ja) * 1984-03-01 1985-09-19 Nippon Shokubai Kagaku Kogyo Co Ltd ペンタフルオロベンゾニトリルの製造方法
JPS60228436A (ja) * 1984-04-27 1985-11-13 Asahi Glass Co Ltd 芳香族化合物のフツ素化方法
US4590315A (en) * 1984-10-15 1986-05-20 Occidental Chemical Corporation Process for the preparation of halo aromatic compounds
GB8504268D0 (en) * 1985-02-19 1985-03-20 Shell Int Research Preparation of fluorinated pyridines
DE3700779A1 (de) * 1986-01-16 1987-08-06 Ciba Geigy Ag Verfahren zur herstellung von 2,3-difluor-5-chlorpyridin

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3992432A (en) * 1967-04-05 1976-11-16 Continental Oil Company Phase transfer catalysis of heterogeneous reactions by quaternary salts
EP0003344A1 (fr) * 1978-01-26 1979-08-08 BASF Aktiengesellschaft Procédé de préparation de fluorobenzènes
DE2938939A1 (de) * 1978-10-05 1980-04-17 Boots Co Ltd Verfahren zur herstellung von fluornitrobenzolen
GB2039473A (en) * 1979-01-11 1980-08-13 Dow Chemical Co Reaction of a chlorinated pyridine with an alkali metal fluoride
JPS57197226A (en) * 1981-05-30 1982-12-03 Dainippon Ink & Chem Inc Preparation of aromatic fluorine compound
JPS60130537A (ja) * 1983-12-16 1985-07-12 Asahi Glass Co Ltd 芳香族フツ素化合物の製法
JPS6165830A (ja) * 1984-09-06 1986-04-04 Daikin Ind Ltd フルオロ有機化合物の製法
WO1987004151A1 (fr) * 1986-01-06 1987-07-16 Mallinckrodt, Inc. Preparation de composes fluoroaromatiques dans une dispersion de fluorure de potassium

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Band 10, Nr. 230 (C-365)(2286), 9. August 1986; & JP 61065830 A (DAIKIN IND. LTD.) 04.04.1986 *
PATENT ABSTRACTS OF JAPAN, Band 7, Nr. 46 (C-153)(1191), 23. Februar 1983; & JP 57197226 A (DAINIPPON INK. K.K.) *
PATENT ABSTRACTS OF JAPAN, Band 9, Nr. 287 (C-314)(2010), 14. November 1985; & JP 60130537 A (ASAHI GLASS K.K.) 12.07.1985 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5237087A (en) * 1991-09-21 1993-08-17 Hoechst Aktiengesellschaft Process for the preparation of chlorinated and fluorinated benzene compounds by selective nucleophilic fluorodenitration
EP0534317A1 (fr) * 1991-09-21 1993-03-31 Hoechst Aktiengesellschaft Procédé de préparation de composés du benzène chlorés et fluorés par fluorodénitration nucléophile sélective
EP0781757A1 (fr) * 1991-10-31 1997-07-02 Abbott Laboratories Procédé de préparation d'acides benzoiques fluorés
US6075165A (en) * 1993-01-19 2000-06-13 Bayer Aktiengesellschaft Process for the preparation of polyhalogenated benzotrifluorides, benzotrichlorides and benzoyl chlorides and new trihalogenobenzotrichlorides and -benzoyl chlorides
EP0781747A1 (fr) * 1993-01-19 1997-07-02 Bayer Ag Procédé pour la préparation de 2,3,4,5-tétrafluoro-trifluorométhylbenzène
US6114590A (en) * 1993-01-19 2000-09-05 Bayer Aktiengesellschaft Process for the preparation of polyhalogenated benzotrifluorides, benzotrichlorides and benzoyl chlorides and new trihalogenobenzotrichlorides and -benzoyl chlorides
EP0635482A2 (fr) * 1993-07-21 1995-01-25 Hoechst Aktiengesellschaft Procédé pour la préparation de polyfluoronitrobenzènes
EP0635482A3 (fr) * 1993-07-21 1996-08-21 Hoechst Ag Procédé pour la préparation de polyfluoronitrobenzènes.
US6300511B1 (en) 1997-07-18 2001-10-09 F2 Chemicals Limited Catalyzed fluorination of carbonyl compounds
WO1999003802A1 (fr) * 1997-07-18 1999-01-28 F2 Chemicals Limited Fluoration catalysee de composes carbonyles
EP0899256A3 (fr) * 1997-08-26 1999-05-19 Nippon Shokubai Co., Ltd. Procédé de préparation de composés organiques fluorés
EP0899256A2 (fr) * 1997-08-26 1999-03-03 Nippon Shokubai Co., Ltd. Procédé de préparation de composés organiques fluorés
US6392084B1 (en) * 1997-08-26 2002-05-21 Nippon Shokubai Co., Ltd. Method for production of organic fluorine compound
EP1233010A1 (fr) * 1997-08-26 2002-08-21 Nippon Shokubai Co., Ltd. Procédé de préparation de composés organiques fluorés
EP1097914A2 (fr) * 1999-11-05 2001-05-09 Clariant GmbH Procédé de traitement de mélanges réactionnels, obtenu par des réactions d' échange d' halogènes
EP1097914A3 (fr) * 1999-11-05 2002-01-23 Clariant GmbH Procédé de traitement de mélanges réactionnels, obtenu par des réactions d' échange d' halogènes

Also Published As

Publication number Publication date
US4978769A (en) 1990-12-18
JP2847786B2 (ja) 1999-01-20
DE58903330D1 (de) 1993-03-04
EP0354444B1 (fr) 1993-01-20
DE3827436A1 (de) 1990-02-15
EP0354444A3 (en) 1990-08-01
JPH0291029A (ja) 1990-03-30

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